YU-ISSN 0352-5139
J.Serb.Chem.Soc. Vol. 65, No. 10(2000)
CONTENTS
Organic Chemistry
E. A. Djurendi}, G. Gy. Vastag, T. M. Suranji, M. M. Popsavin and K. Penov-Ga{i: Synthesis of some bis- and mono-2-hydroxybenzoic acid derivatives and the determination of their acidity constants
681
K. Bowden and G. P. Stevens: An alternative synthesis of clinddamycin
691
Phisical Chemistry
K. Jankovska, L. [optrajanova and I. Spirevska: Protonation of maleic and fumaric acid in aqueous sulfuric acid solutions
695
S. Blagojevi}, N. Peji}, S. Ani} and Lj. Kolar-Ani}: Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition
709
A. Dakovi}, M. Toma{evi}-^anovi}, V. Dondur, A. Vujakovi} and P. Rado{evi}: Kinetics of aflatoxin B1 and G2 adsorption on Ca-clinoptilolite
715
T. J. Janji}, G. Vu~kovi} and M. B. ]elap: Influence of the stationary and mobile phase composition in ideal chromatographic system on the log k values in column chromatography. I. ODS/methanol-water-system
725
T. J. Janji}, G. Vu~kovi} and M. B. ]elap: Application of the log k pair linearity rule and Proportionality rule to the RPP mobile phase scales estimation on diol-silica-column
733
J. Petkovi}, I. Mladenovi}, N. Vukeli}, M. Mojovi} and G. Ba~i}: Lanthanide doped alkaline metal sulphates as candidates for EPR dosimetry
743
Chemical Engineering
A. Moise and R. Z. Tudose: An experimental study of the drying granular materials in a packed bed passed by hot air. The local humidity of the material
755
J.Serb.Chem.Soc.65(10)681–689(2000)
UDC 547.582.4:542.9:541.12.03
JSCS-2792
Original scientific paper
Synthesis of some bis- and mono-2-hydroxybenzoic acid
derivatives and the determination of their acidity constants
EVGENIJA A. DJURENDI] , GYÖNGYI GY. VASTAG#, TERÉZIA M. SURÁNYI#, MIRJANA M. POPSAVIN# and KATARINA M. PENOV GA[I#
Institute of Chemistry, Faculty of Sciences, University of Novi Sad, Trg D. Obradovi}a 3, YU-21000 Novi Sad, Yugoslavia
(Received 21 March, revised 14 June 2000)
Several bis- and mono-2-hydroxybenzoic acid derivatives were synthesized by the reaction of methyl 2-hydroxybenzoate with some alcohols (diols, polyols and amino alcohols) and their acidity constants were determined in 60 % aqueous ethanol by the potentiometric titration method. It has been shown that the biochemical behaviour of these compounds is greatly dependent on their acidity. It appears that the ester derivatives are weaker acids than the amide derivatives and, therefore, can be potentially more involved in the processes of metal ions transport in plants, whereas the introduction of –OH and –CH3 groups has a very small effect on the biochemical properties.
Keywords: 2-hydroxybenzoic acid derivatives, synthesis, acidity constants.
IZVOD
SINTEZA NEKIH BIS- I MONO-DERIVATA 2-HIDROKSIBENZOEVE KISELINE I ODRE\IVAWE WIHOVIH KISELINSKIH KONSTANTI
EVGENIJA A. \URENDI], \EN\I \. VA[TAG, TEREZIJA M. [URAWI,
MIRJANA M. POPSAVIN i KATARINA M. PENOV GA[I
Institut za hemiju, Prirodno-matemati~ki fakultet, Univerzitet u Novom Sadu, Trg D. Obradovi}a 3, 21000 Novi Sad
Sintetizovani su bis- i mono-derivati 2-hidroksibenzoeve kiseline reakcijom metil-2-hidroksibenzoata i alkohola (diola, poliola i amino alkohola) i odre|ene su wihove kiselinske konstante u 60 %-nom etanolu, potenciometrijskom titracijom. Pokazalo se da estarski derivati usled slabije kiselosti mogu da u~estvuju u ve}oj meri u procesu transporta jona metala u biqkama nego amidni derivati.
(Primqeno 21. marta, revidirano 14. juna 2000)
REFERENCES
1. R. A. Olsen, J. C. Brown, J. H. Bennett, D. Bloom, J. Plant Nutr. 5 (1982) 433
2. D. A. Miljkovi}, E. A. Djurendi}, T. M. Surányi, Rev. Res (Faculty of Science, University of Novi Sad) 13 (1983) 5
3. E. A. Djurendi}, T. M. Surányi, D. A. Miljkovi}, Collect. Czech. Chem. Commun. 55 (1990) 1763
4. E. A. Djurendi}, T. M. Surányi, D. A. Miljkovi}, Collect. Czech. Chem. Commun. 56 (1991) 1446
5. T. M. Surányi, E. A. Djurendi}, Gy. Gy. Vastag, Collect. Czech. Chem. Commun. 60 (1995) 464
6. Gy. Gy. Vastag, T. M. Surányi, E. A. Djurendi}, J. Serb. Chem. Soc. 62 (1997) 335
7. T. M. Surányi, E. A. Djurendi}, D. A. Miljkovi}, J. Serb. Chem. Soc. 53 (1988) 551
8. A. S. Brown, J. Am. Chem. Soc. 56 (1934) 646
9. B. Gutbezahl, E. Grunwald, J. Am. Chem. Soc. 75 (1953) 565
10. L. Zékány, J. D. Nagypál, PSEQUAD, A Comprehensive Program for the Evaluation of Potentiometric and/or Spectrophotometric Equilibrium Data Using Analytical Derivatives“, in Computational Methods for the Determination of Formation Constants. D. J. Leggett, Ed., Plenum Press, New York, 1985, p. 291.
J.Serb.Chem.Soc.65(10)691–694(2000)
UDC 615.28/.281
JSCS–2793
Original scientific paper
An alternative synthesis of clindamycin
KEITH BOWDEN and GRAHAM P. STEVENS
Department of Biological and Chemical Sciences, Central Campus, University of Essex, Wivenhoe Park, Colchester, Essex, UK, CO4 3SQ
(Received 7 June 2000)
A novel synthesis of clindamycin from lincomycin using N-chlorosuccinimide and triphenylphosphine is reported. This results in high yields and avoids the use of tetrachloromethane employed in the current manufacturing process.
Keywords: clindamycin, N-chlorosuccinmide.
IZVOD
ALTERNATIVNA SINTEZA KLINDAMICINA
KEITH BOWDEN and GRAHAM P. STEVENS
Department of Bilogical and Chemical Sciences, Central Campus, University of Essex, Wivenhoe Park,
Colchester, Essex, UK, CO4 3SQ
Prikazana je nova sinteza klindamicina polaze}i od linkomicina kori{}ewem N-hlorosikcinimida i trifenilfosfina. Ovim se dobijaju visoki prinosi i izbegava kori{}ewe tetrahlormetana kao {to je sada slu~aj u procesima proizvodwe klindamicina.
(Primqeno 7. juna 2000)
REFERENCES
1. R. D. Birkenmeyer, U.S. Patent 3,435,025, March 25, 1969 (C. A. 71 (1969) 81696x)
2. J. E. F. Reynolds, Ed., Martindale. The Extra Pharmacopoeia, 29th Edn., The Pharmaceutical Press, London, 1989
3. R. D. Birkenmeyer, F. Kagan, J. Med. Chem. 13 (1970) 616
4. G. A. Wiley, R. L. Hershkowitz, R. B. Rein, B. C. Chung, J. Am. Chem. Soc. 86 (1964) 964
5. G. A. Wiley, B. J. Rein, R. L. Hershkowitz, Tetrahedron Lett. 36 (1964) 2509
6. J. B. Lee, I. M. Downie, Tetrahedron 23 (1967) 359
7. D. Brett, I. M. Downie, J. B. Lee, J. Org. Chem. 32 (1967) 855
8. R. D. Birkenmeyer, U. S. Patent 3,475,407, Oct 28, 1969 (C. A. 73 (1970) 25835w)
9. D. R. Hepburn, H. R. Hudson, J. Chem. Soc. Perkin Trans. 1 (1976) 754
10. R. M. Magid, O. S. Fruchey, W. L. Johnson, T. G. Allen, J. Org. Chem. 44 (1979) 359; R. M. Magid, B. G. Talley, S. K. Souther, J. Org. Chem. 46 (1981) 824.
J.Serb.Chem.Soc.65(10)695–708(2000)
UDC 547.462.3:539.172.3
JSCS–2794
Original scientific paper
Protonation of maleic and fumaric acid in aqueous
sulfuric acid solutions
KATICA JANKOVSKA1, LIDIJA [OPTRAJANOVA2 and ILINKA SPIREVSKA2
1Faculty of Metallurgy and Technology, Rudjer Bo{kovi} bb, 91000 Skopje, Macedonia and
2Institute of Chemistry, Faculty of Natural Sciences and Mathematics, P.O. Box 162, 91001 Skopje, Macedonia
(Received 26 January, revised 12 June 2000)
The protonations of maleic and fumaric acid in an acidic medium (aqueous solutions of sulfuric acid) were followed spectrophotometrically at room temperature. The acid-base equilibria were characterised qualitatively and quantitatively. The pKBH+ values were determined using the Hammett equation, employing several acid functions in order to determine which of them describes best the protonation process of the studied organic acids. The thermodynamic pKBH+ values as well as those of the solvation parameters m, m* and f and of the thermodynamic protonation constants (or, rather, the pKa,p values) were also defermined. The method of characteristic vector analysis (CVA) was used to reconstruct the experimental spectra.
Keywords: maleic acid, fumaric acid, protonation, spectrophotometry.
IZVOD
PROTONIRAWE MALEINSKE I FUMARNE KISELINE U VODENOM RASTVORU SUMPORNE KISELINE
KATICA JANKOVSKA, LIDIJA [OPTRAJANOVA i ILINKA SPIREVSKA
1Tehnolo{ko-metalur{ki fakultet, Ru|er Bo{kovi} bb, 911000 Skopje i 2Institut za hemiju, Prirodno-matemati~ki fakultet, Univerzitet “Sv. Kiril i Metodij, p. pr. 106, 91000 Skopje, Republika Makedonija
Spektrofotometrijskom metodom, na sobnoj temperaturi, pra}eno je protonirawe maleinske i fumarne kiseline u kiseloj sredini (vodeni rastvor sumporne kiseline). Date su i kvalitativna i kvantitativna karakteristika nastale acido-bazne ravnote`e. pKBH+ vrednost je izra~unata primenom Hametove jedna~ine pri ~emu su kori{}ene razli~ite kiselinske funkcije da bi se utvrdilo koja od wih najboqe karakterizira proces protonirawa ispitivanih organskih kiselina. Izra~unate su i termodinami~ke pKBH+ vrednosti, vrednosti solvatacionih parametar m, m* i f kao i termodinami~ke konstante protonirawa (pKa,p vrednosti). Za rekonstrukciju eksperimentalnih spektara, primewena je metoda karakteristi~ne vektorske analize (CVA).
(Primqeno 26. junuara, revidirano 12. juna 2000)
REFERENCES
1. I. Jacson, R. Herman, Eur. Pat. Appl. EP. 387 (1990) 219
2. W. D. Robinson, R. A. Mount, Kirk-Othmer, Encycl. Chim. Technol., 3rd ed., M. Grysocu, New York, 1981, p. 14, 770
3. C. Das, U. N. Dach, K. N. Panda, J. Chem. Soc. Faraday Trans. 76 (1980) 2152
4. W. Simon, D. Menche, E. Heillbronner, Helv. Chim. Acta. 39 (1956) 290
5. L. Pospi{il, J. Tomanova, J. Kuta, Collect. Czech. Chem. Commun. 33 (1968) 594
6. L. Pospi{il, J. Kuta, Collect. Czech. Chem. Commun. 34 (1969) 742
7. L. P. Hammett, A. J. Deyrup, J. Am. Chem. Soc. 54 (1932) 2721
8. W. Larsen, P. A. Bouis, J. Org. Chem. 38 (1973) 1415
9. L. M. Benoit, A. G. Harrison, J. Am. Chem. Soc. 99 (1977) 3980
10. A. M. Amat, G. Asensio, M. J. Castello, M. A. Miranda, A. Simon-Fuentes, Tetrahedron 43 (1987) 905
11. K. Jankovska, Ph. D. Thesis, University of Skopje, 1997, Skopje
12. M. A. Poul, F. A. Long, Chem. Rev. 57 (1957) 1
13. T. G. Bonner, J. Philips, J. Chem. Soc. (B) (1966) 650
14. K. Yates, J. B. Stevans, A. R. Katritzky, Can. J. Chem. 42 (1964) 1957
15. K. Yates, R. A. McClelland, J. Am. Chem. Soc. 89 (1967) 2686
16. J. F. Bunnett, F. P. Olsen, Can. J. Chem. 44 (1966) 1899
17. R. A. Cox, K. J. Yates, J. Am. Chem. Soc. 100 (1978) 3861
18. K. Seyda, Polish J. Chem. 57 (1983) 1313
19. C. T. Davis, T. A. Geissman, J. Am. Chem. Soc. 76 (1954) 3507
20. R. I. Zalewski, J. Chem. Soc. Perkin Trans. II (1979) 1637
21. T. E. Edward, S. C. Wong, J. Am. Chem. Soc. 99 (1977) 4229.
22. I. Spirevska, L. Soptrajanova, B. Andonovski, Glas. Hem. Technol. Macedonia 8 (1990)151
23. L. Soptrajanova, I. Spirevska, Glas. Hem. Technol. Macedonia 10 (1991) 21
24. I. Spirevska, L. Soptrajanova, K. Jankovska, B. Andonovski, J. Mol. Struct. 93 (1993) 293
25. C. D. Johnson, A. R. Katritzky, B. J. Ridgewell, N. Shakir, A. M. White, Tetrahedron 21 (1965) 1055
26. C. C. Greeg, C. D. Johnson, J. Am. Chem. Soc. 90 (1968) 6453
27. E. M. Arnett in Progress in Physical Organic Chemistry, Vol. 1, S. G. Cohen, A. Streitwieser and R. W. Taft, Eds. Interscience, New Yoprk, 1963
28. A. Bagno, G. Scorrano, R. A. More O Ferrall, Rev. Chem. Intermed 7 (1987) 313
29. V. Lucchini, G. Modena, G. Scorrano, R. A. Cox, K. Yates, J. Am. Chem. Soc. 104 (1982) 1958
30. E. M. Arnett in Proton Transfer Reactions, E. F. Caldin and V. Gold, Eds., Chapman and Hall, London, 1975
31. A. Levi, G. Modena, G. Scorrano, J. Am. Chem. Soc. 96 (1974) 6585
32. M. Lj. Mihailovi}, Osnovi teorijske organske hemije i stereo hemije, Gradjevinska knjiga, Beograd, 1970 (in Serbian).
J.Serb.Chem.Soc.65(10)709–713(2000)
UDC 547.461.3:539.173:541.127
JSCS–2795
Original scientific paper
Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition
SLAVICA BLAGOJEVI],1 NATA[A PEJI],1 SLOBODAN ANI]2 and
LJILJANA KOLAR-ANI]2
1Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, YU-11000 Belgrade and
2Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, P. O. Box 137, YU-11001 Belgrade, Yugoslavia
(Received 26 April 2000)
The kinetics of the Belousov-Zhabotinsky (BZ) oscillatory reaction was analyzed. With this aim, the time evolution of a reaction mixture composed of malonic acid, bromate, sulfuric acid and cerium(III) was studied at 298 K. Pseudo-first order kinetics with respect to malonic acid as the species undergoing decomposition with a corresponding rate constant, k = 7.5´10-3 min-1, was found.
Keywords: kinetics, non-linear dynamics, oscillatory reaction, Belousov-Zhabotinsky reaction.
IZVOD
BELOUSOV-@ABOTINSKI OSCILATORNA REAKCIJA. KINETIKA RAZLAGAWA MALONSKE KISELINE
SLAVICA BLAGOJEVI],1 NATA[A PEJI],1 SLOBODAN ANI]2 i QIQANA KOLAR-ANI]2
1Farmaceutski fakultet, Vojvode Stepe 450, 11000 Beograd i 2Fakultet za fizi~ku hemiju, Studentski trg 12-16, p. pr. 137, 11001 Beograd
Sa ciqem da se analizira kinetika Belousov-@abotinski oscilatorne reakcije, prou~avana je vremenska evolucija reakcione sme{e koja se sastoji od malonske kiseline, sumporne kiseline i cerijuma(III) na 298 K. Na|ena je kinetika pseudo-prvog reda u odnosu na malonsku kiselinu kao vrstu koja podle`e razlagawu i odgovaraju}a konstanta brzike, k = 7.5´10-3 min-1.
(Primqeno 26. aprila 2000)
REFERENCES
1. B. P. Belousov, Sb. Ref. Radiats. Med. (Madgiz, Moskow) 1 (1958) 145
2. A. M. Zhabotinski, Biofizika 9 (1963) 306
3. R. J. Fild, M. Burger, Oscillations and Traveling Waves in Chemical System, Mir, Moscow, 1988, pp. 78 – 116
4. K. Showalter, J. Chem. Phys. 73 (1980) 3735
5. E. Körös, M. Orban, Z. Nagy, J. Phys. Chem. 77 (1973) 3122
6. E. Hansen, P. Ruoff, J. Phys. Chem. 93 (1989) 2696
7. E. Körös, Oscillations, Waves and Spirals in Chemical Systems, World Scientific, London, 1992, p.p. 221 – 242
8. R. J. Field, E. Körös, R. M. Noyes, J. Am. Chem. Soc. 94 (1972) 8649
9. C. Herbo, G. Schmitz, M. Glabbeke, Can. J. Chem. 54 (1976) 2628
10. R. M. Noyes, J. Am. Chem. Soc. 102 (1980a) 4644
11. M. Burger, E. Körös, J. Phys. Chem. 84 (1980) 496
12. E. Körös, Nature 251 (1974) 703
13. S. Ani}, Lj. Kolar-Ani}, Ber. Bunsenges. Phys. Chem. (a) 90 (1986) 539
14. S. Ani}, Lj. Kolar-Ani}, J. Chem. Soc. Faraday Trans. I 84 (1988) 3413
15. S. Ani}, D. Stanisavljev, J. Serb. Chem. Soc. 61 (1996) 125
16. S. Ani}, V. Vukojevi}, M. Radenkovi}, Lj. Kolar-Ani}, J. Serb. Chem. Soc. 54 (1989) 521.
J. Serb. Chem. Soc. 65(10)715–723(2000)
UDC 632.952:541.183:549.67:582.28
JSCS-2796
Original scientific paper
Kinetics of aflatoxin B1 and G2 adsorption on Ca-clinoptilolite
ALEKSANDRA DAKOVI], MAGDALENA TOMA[EVI]-^ANOVI], VERA DONDUR1, ALEKSANDRA VUJAKOVI] and PREDRAG RADO[EVI]
Institute for Technology of Nuclear and Other Mineral Raw Materials, P. O. Box 390, YU-11001, Belgrade, and 1Faculty of Physical Chemistry, P. O. Box 137, YU-11001 Belgrade, Yugoslavia
(Received 26 March 2000)
The kinetics of aflatoxins B1 and G2 adsorption on Ca-clinoptilolite at pH 2 and 7, in aqueous electrolyte at 37 ºC were studied. For both aflatoxins, the adsorption process begins with a fast reaction whereby most of the toxin is adsorbed in the first few minutes. This fast process is followed by the significantly slower process of aflatoxin bonding at active centers of mineral adsorbent. The initial rate method showed that the fast adsorption process of aflatoxin B1 and G2, at both pH values is a first order reaction, while the slow adsorption process of these aflatoxins is a zero order reaction. The adsorption indexes and adsorption rates for both examined toxins were pH dependent. In the investigated initial toxins concentration ranges (500–3000 mg/dm3), high adsorption indexes were achieved (> 80 %).